Search results for "electron transfer"

A pseudo-Jahn–Teller model of the photochromic effect in sodium nitroprusside

2003

Abstract A new model for the photochromic effect in sodium nitroprusside Na2[Fe(CN)5(NO)]·2H2O based on the concept of the pseudo-Jahn–Teller effect is proposed. The model takes into account the electron transfer from the Fe2+ ion to the π* orbitals of the NO-ligand as well as the vibronic mixing of three electronic states of the Fe NO fragment through the non-symmetric and full-symmetric modes. The problem is solved within the adiabatic approximation. Under certain conditions the lower sheet of the adiabatic potential is shown to possess three minima with the increasing energies that correspond to the N-bound, sideways bound and O-bound NO group. The barriers between the minima are estimat…

A Bis(tridentate)cobalt Polypyridine Complex as Mediator in Dye‐Sensitized Solar Cells

2015

Dye-sensitized solar cells equipped with cationic and neutral RuII-based sensitizers [Ru(ddpd){tpy(COOH)3}]2+ [12+; ddpd = N,N′-dimethyl-N,N′-di(pyridin-2-yl)pyridin-2,6-diamine, tpy(COOH)3 = 2,2″6′,2″-terpyridine-4,4′,4″-tricarboxylic acid] and [Ru(ddpd){tpy(COOH)(COO)2}] (2) with and without the coadsorbent chenodeoxycholic acid were constructed with I3–/I– or the CoIII/II-based redox mediators [Co(bpy)3]3+/2+ (33+/2+; bpy = 2,2′-bipyridine) and [Co(ddpd)2]3+/2+ (43+/2+) in the presence of LiClO4 and 4-tert-butylpyridine. The best photovoltaic performance was achieved by using the 43+/2+ shuttle and the neutral sensitizer 2 without coadsorbent. The higher short-circuit photocurrent densit…

Proton and Electron Transfer to a Polymer‐Supported Nitrido Molybdenum(VI) Complex (Eur. J. Inorg. Chem. 36/2013)

2013

Proton and Electron Transfer to a Polymer‐Supported Nitrido Molybdenum(VI) Complex

2013

Invited for the cover of this issue is the group of Katja Heinze at Johannes Gutenberg University of Mainz, Germany. The cover image shows the reactive imido molybdenum(V) intermediate that has been obtained by protonation followed by reduction of the nitrido molybdenum(VI) precursor anchored to a polymeric environment.

Electron Transfer and Conformational Interconversions in 1, n ‐Diphenylpolyenes

1988

1,4-Diphenylbutadiene (1), 1,6-diphenylhexatriene (2), and 1,8-diphenylocatatetraene (3) are reduced with alkali metals and the resulting paramagnetic monoanions and diamagnetic dianions characterized by ESR and (1H-, 13C-)NMR spectroscopy, respectively. The stereodynamic behavior of the ions is studied as a function of chain length, charge, and counterion. The reduction of 1, 2, and 3 serves as a model experiment for the doping of extended linear polyenes (polyacetylenes). Elektronenubertragungen und Konformationsanderungen in 1,n-Diphenylpolyenen 1,4-Diphenylbutadien (1), 1,6-Diphenylhexatrien (2) und 1,8-Diphenyloctatetraen (3) werden mit Alkalimetallen reduziert, und die resultierenden …

Tuning Reductive and Oxidative Photoinduced Electron Transfer in Amide‐Linked Anthraquinone–Porphyrin–Ferrocene Architectures

2014

Porphyrin amino acids 3a–3h with meso substituents Ar of tunable electron-donating power (Ar = 4-C6H4OnBu, 4-C6H4OMe, 4-C6H4Me, Mes, C6H5, 4-C6H4F, 4-C6H4CF3, C6F5) have been linked at the N terminus to anthraquinone Q as electron acceptor through amide bonds to give Q-PAr dyads 4a–4h. These were conjugated to ferrocene Fc at the C terminus as electron donor to give the acceptor-chromophore-donor Q-PAr-Fc triads 6a–6h. To further modify the energies of the electronically excited and charge-separated states, the triads 6a–6h were metallated with zinc(II) to give the corresponding Q-(Zn)PAr-Fc triads Zn-6a–Zn-6h. The Q-PAr1 dyad (Ar1 = C6H5) was further extended with a second porphyrin PAr2 (…

A New ZnIITweezer Pyridine-Naphthalene System - An Off-On-Off System Working in a Biological pH Window

2005

Their basic idea consisted of the connec-tion of an amine to a fluorophoric anthracene unit on oneside and to a pyridine moiety on the other. At acidic pHvalues the amino and the pyridine groups are protonatedand a photoinduced electron transfer (PET) occurs fromthe π-π* excited state of the anthracene to the protonatedpyridinium unit, leading to quenching of the fluorescence.However, at high pH values, where the amino group is notprotonated, PET alternatively takes place from the aminelone pair to the same excited state of the fluorophore, yield-ing the same inhibitory effect on the fluorescence. Betweenthese two pH values, there is a pH window where PET doesnot take place and fluorescence…

Aminoferrocene and Ferrocene Amino Acid as Electron Donors in Modular Porphyrin–Ferrocene and Porphyrin–Ferrocene–Porphyrin Conjugates

2014

New amide-linked porphyrin–ferrocene conjugates [M(PAr)–Fc] were prepared from aminoferrocene and a carboxy-substituted meso-tetraaryl-porphyrin [M = 2H, Zn; Ar = mesityl (Mes), C6F5: 3a, 3e, Zn-3a, Zn-3e]. A further porphyrin building block was attached to the second cyclopentadienyl ring of the ferrocene moiety to give the metallopeptides M(PMes)–Fc–M(PAr) (M = 2H, Zn; Ar = C6H5, 4-C6H4F: 6b, 6c, Zn-6b, Zn-6c). The effects of the Ar substituents, the porphyrin central atom M and the presence of the second porphyrin at the ferrocene hinge on the excited-state dynamics was studied by optical absorption spectroscopy, electrochemistry, steady-state emission, time-resolved fluorescence measure…

Electrochemical and Electronic Structure Investigations of the [S3N3]• Radical and Kinetic Modeling of the [S4N4]n/[S3N3]n (n = 0, −1) Interconversion

2009

Voltammetric studies of S4N4 employing both cyclic (CV) and rotating disk (RDE) methods in CH2Cl2 at a glassy carbon electrode reveal a one-electron reduction at −1.00 V (versus ferrocene/ferrocenium), which produces a second redox couple at −0.33 V, confirmed to be the electrochemically generated [S3N3]− by CV studies on its salts. Diffusion coefficients (CH2Cl2/0.4 M [nBu4N][PF6]) estimated by RDE methods: S4N4, 1.17 × 10−5 cm2 s−1; [S3N3]−, 4.00 × 10−6 cm2 s−1. Digital simulations of the CVs detected slow rates of electron transfer for both couples and allowed for a determination of rate constants for homogeneous chemical reaction steps subsequent to electron transfer. The common paramet…

Dynamics of closure of zinc bis-porphyrin molecular tweezers with copper(II) ions and electron transfer.

2011

Zinc bis-porphyrin molecular tweezers composed of a N(4) spacer bound through pyridyl units to the meso position of porphyrins were synthesized, and the tweezers are closed by the coordination of a copper(II) ion inside the spacer ligand. The effect of the π-π interaction between the porphyrin rings in the closed conformation on the absorption spectra of multi-electron oxidized species and the reduction potentials were clarified by chemical and electrochemical oxidation of the closed form of the zinc bis-porphyrin molecular tweezers in comparison with the open form without copper(II) ion and the corresponding porphyrin monomer. The shifts in redox potentials and absorption spectrum of the p…